WO2005087866A1 - Organopolysiloxane-containing graft copolymer composition - Google Patents
Organopolysiloxane-containing graft copolymer composition Download PDFInfo
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- WO2005087866A1 WO2005087866A1 PCT/JP2005/003632 JP2005003632W WO2005087866A1 WO 2005087866 A1 WO2005087866 A1 WO 2005087866A1 JP 2005003632 W JP2005003632 W JP 2005003632W WO 2005087866 A1 WO2005087866 A1 WO 2005087866A1
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- organopolysiloxane
- graft copolymer
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- containing graft
- copolymer composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Definitions
- the present invention relates to an organopolysiloxane-containing graft copolymer composition, a flame retardant comprising the above graft copolymer composition, and a flame retardant resin composition containing the above graft copolymer composition.
- Polycarbonate resins are widely used as electric and electronic parts, OA equipment, household goods, and building materials because of their excellent impact resistance, heat resistance, and electrical properties. Polycarbonate resins have higher flame retardancy than polystyrene resins, etc.There are fields where high flame retardancy is required, especially in fields such as electric and electronic parts and OA equipment. In addition, various types of flame retardants have been used to improve the properties, and in recent years, studies on non-halogen and non-phosphorus flame retardants have been conducted.
- a method of obtaining an impact-resistant flame-retardant resin composition by using an organopolysiloxane compound is to use a butyl rubber as a composite rubber, which has an organopolysiloxane rubber and a polyalkyl (meth) atalylate rubber, and a strong rubber.
- thermoplastic rubber with a composite rubber-based flame retardant obtained by graft polymerization of a polymer see Patent Document 1, for example
- a composite particle of an organopolysiloxane having an aromatic group and a butyl polymer Blending an organopolysiloxane-based flame retardant grafted with a thermoplastic resin see, for example, Patent Document 2
- an organopolysiloxane obtained by graft-polymerizing a vinyl-based monomer onto organopolysiloxane particles of 0.2 m or less A method of blending a siloxane-containing graft copolymer with a thermoplastic resin (for example, see Patent Documents 3 and 4) is known.
- Patent Document 5 in order to measure the performance improvement such as high durability and high resolution of the conductive layer in order to apply to the photosensitive layer conductive layer material in the electrophotographic technology, the obtained graft is used.
- a method has been proposed in which the polymer is purified using warm water, alcohol, or the like to reduce the electrolyte content in the graft copolymer.
- Patent Document 1 JP-A-2000-17029
- Patent Document 2 JP-A-2000-226420
- Patent Document 3 JP-A-2000-264935
- Patent Document 4 JP 2002-348453 A
- Patent Document 5 JP-A-2002-105122
- the present invention provides an organopolysiloxane-containing graft copolymer composition excellent in flame retardancy and impact resistance improving effects, a non-halogen non-phosphorous flame retardant, and the graft copolymer composition.
- An object of the present invention is to provide a resin composition having excellent flame retardancy and impact resistance.
- the inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an organopolysiloxane-containing graft containing a halogen atom, an alkaline earth metal atom, and an alkali metal salt of a sulfur-containing organic compound in specific amounts, respectively.
- the present inventors have found that the above object can be achieved by the copolymer composition, and have completed the present invention.
- the present invention provides:
- organopolysiloxane-containing graft copolymer (A) is composed of 100 parts by weight of the organopolysiloxane-containing graft copolymer (A) and an alkali metal salt of a sulfur-containing organic compound (B) O. 02-3.5 parts by weight, and has a halogen atom content of ⁇ pm or less. And an organopolysiloxane-containing graft copolymer composition having an alkaline earth metal atom content of 3000 ppm or less.
- the present invention relates to 100 parts by weight of an organopolysiloxane-containing graft copolymer having a halogen atom content of 100 ppm or less and an alkaline earth metal atom content of 3000 ppm or less, and 100 parts by weight of a sulfur-containing organic compound.
- the present invention relates to an organopolysiloxane-containing graft copolymer composition obtained by adding 0.02 to 3.5 parts by weight of an alkali metal salt of a compound (B).
- the present invention provides a method wherein the organopolysiloxane-containing graft copolymer (A) is in a latex state.
- Polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule in the presence of the organopolysiloxane (C) (D) 100-50% by weight and other copolymerizable monomers (E)
- the present invention relates to a siloxane-containing graft copolymer composition.
- the embodiment is characterized in that the organopolysiloxane-containing graft copolymer (A) has a halogen atom content of 100 ppm or less and an alkaline earth metal atom content of 3000 ppm or less.
- the present invention relates to an organopolysiloxane-containing graft copolymer composition.
- an organopolysiloxane-containing graft copolymer composition is characterized in that an alkali metal salt (B) of a sulfur-containing organic compound is added to the organopolysiloxane-containing graft copolymer (A).
- B alkali metal salt of a sulfur-containing organic compound
- a preferred embodiment relates to an organopolysiloxane-containing graft copolymer composition having an alkaline earth metal content of 200 to 3000 ppm.
- a preferred embodiment relates to an organopolysiloxane-containing graft copolymer composition, wherein the alkaline earth metal is calcium.
- the embodiment relates to an organopolysiloxane-containing graft copolymer composition, wherein the organopolysiloxane-containing graft copolymer (A) has been washed with a solvent.
- a preferred embodiment relates to an organopolysiloxane-containing graft copolymer composition, wherein the solvent is water and Z or an alcohol having 4 or less carbon atoms.
- the organopolysiloxane-containing graft copolymer is characterized in that the organopolysiloxane-containing graft copolymer (A) is washed with 70 times or less by weight of water. It relates to a polymer composition.
- the organopolysiloxane-containing graft copolymer (I) is preferably, as an embodiment, the organopolysiloxane-containing graft copolymer (I)
- the present invention relates to an organopolysiloxane-containing graft copolymer composition which has been washed with water at a temperature lower than 0 ° C. [0018]
- the present invention also relates to a method for producing the above graft copolymer composition.
- the present invention also relates to a flame retardant comprising the above-described graft copolymer composition.
- the present invention also relates to the above-described resin composition containing a resin selected from a thermoplastic resin, a thermosetting resin, and an elastomer.
- thermoplastic resin is a polycarbonate resin.
- a high level of flame retardancy can be realized even in a thin-walled molded product in which it is difficult to exhibit flame retardancy, and at the same time, excellent impact resistance can be imparted.
- an organopolysiloxane-containing graft copolymer (A) and an alkali metal salt of a sulfur-containing organic compound (B) O. 02-3.5 parts by weight have a halogen atom content of 100 parts by weight.
- the present invention relates to an organopolysiloxane-containing graft copolymer composition containing Oppm or less and having an alkaline earth metal atom content of 3000 ppm or less.
- the organopolysiloxane component in the organopolysiloxane-containing graft copolymer (A) of the present invention is a component that imparts impact resistance and preferably flame retardancy to the final molded article.
- the graft copolymer (A) has 100 parts by weight of an organopolysiloxane-containing graft copolymer having a halogen atom content of 100 ppm or less and an alkaline earth metal atom content of 3000 ppm or less, and a sulfur-containing organic compound.
- the organopolysiloxane-containing graft copolymer (A) of the present invention is preferably a polyfunctional polymer containing two or more polymerizable unsaturated bonds in the molecule, preferably in the presence of the organopolysiloxane (C) in a latex state.
- Polymerizable monomer (D) 100 to 50% by weight and other copolymerizable monomer (E) 0 to 50% by weight of vinyl monomer (F) is polymerized in one or more stages. And further obtained by polymerizing the butyl monomer (G) in one or more stages.
- the organopolysiloxane (C) is preferably at least 30 parts by weight, more preferably at least 50 parts by weight, and preferably at least 95 parts by weight. Parts by weight or less, more preferably 90 parts by weight or less, the vinyl monomer (F) is 0 part by weight or more, preferably 1 part by weight or more, 10 parts by weight or less, preferably 7 parts by weight or less, The monomer (G) is preferably at least 5 parts by weight, more preferably at least 10 parts by weight, preferably at most 70 parts by weight, more preferably at most 50 parts by weight, and the total of (C), (F) and (G) Use to make 100 parts by weight. Use of the organopolysiloxane (C), the vinyl monomer (F), and the vinyl monomer (G) outside the above ranges may simultaneously exhibit flame retardancy and impact resistance. It can be difficult.
- the organopolysiloxane (C) in a latex state is described in JP-A-2000-226420, JP-A-2000-834392, U.S. Pat. It can be obtained by the known emulsion polymerization method described above. That is, a cyclic siloxane represented by 1,3,5,7-otatamethylcyclotetrasiloxane (D4), and a bifunctional silane having a hydrolyzable group such as Z or dimethyldimethoxysilane, if necessary.
- D4 1,3,5,7-otatamethylcyclotetrasiloxane
- a bifunctional silane having a hydrolyzable group such as Z or dimethyldimethoxysilane
- Bifunctional or higher alkoxysilanes such as methyltriethoxysilane and tetrapropyloxysilane, and, if necessary, mercaptopropyldimethoxymethylsilane, methacryloyloxypropyldimethoxymethylsilane, vinyldimethoxymethylsilane, vinylphenyldimethoxymethyl
- a graft crosslinking agent such as silane is preferably emulsified using a homogenizer or the like together with water and a surfactant, and then the acid is added to adjust the pH to 4 or less, preferably 3 or less, more preferably 2 or less, or a base.
- the pH value is 8 or more, preferably 9.5 or more, more preferably 11 or more
- the polymerization temperature is 0 ° C or more, preferably 30 ° C or more, more preferably 50 ° C or more, furthermore, 60 ° C or more, 150 ° C or less, preferably 120 ° C or less, more preferably Or 95 ° C. or lower, preferably under an atmosphere of an inert gas such as nitrogen or in a state of being degassed under vacuum, and can be obtained by a hydrolysis-condensation reaction.
- the organopolysiloxane latex prepared by the above method contains volatile low-molecular-weight cyclic siloxanes, which are disclosed in US Pat. No. 4,600,436 and Japanese Patent Publication No. 2002-249582 for the purpose of removing these.
- a method of adding a sorbent such as diatomaceous earth to adsorb a low-molecular-weight cyclic siloxane and then filtering it off is applied. Or you can.
- the volatile low molecular weight siloxane content is 5% or less, more preferably 1% or less
- the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, even more preferably 3000 or less, the terminal hydroxyl group,
- An amino group, or a hydrolyzable group such as an alkoxyl group or an acyloxy group, and if necessary, a mercaptopropyl group, a methacryloyloxypropyl group, an atalyloyloxypropyl group, a vinyl group, a vinyl group.
- the mixture is mechanically emulsified to a desired particle size, and the polymerization temperature is 0 ° C or higher, preferably 15 ° C or higher, further 25 ° C or higher, preferably 100 ° C or lower, more preferably 70 ° C or lower.
- the content of volatile low-molecular-weight siloxane is small as a raw material! /
- the above-mentioned organopolysiloxane having a reduced volatile low-molecular-weight siloxane can be selected by selecting polymerization conditions. You get C).
- a surfactant that exhibits surface activity even under acidic conditions for example, a metal salt of an alkyl sulfate ester or a metal salt of an alkyl sulfonic acid.
- Anionic surfactants such as salts and metal salts of alkylaryl sulfonic acids can be used.
- the metal salt an alkali metal salt, particularly, a sodium salt or a potassium salt is preferably selected. Most preferred is sodium dodecylbenzenesulfonate.
- polyoxyalkylene alkyl ethers represented by polyoxyethylene dodecyl ether polyoxyalkylene alkyl aryl ethers represented by polyoxyethylene nonylphenyl ether, and polyoxyalkylene higher ethers represented by polyoxyethylene stearic acid ester
- a nonionic surfactant such as a nonionic surfactant such as a fatty acid ester or sorbitan monolaurate may be used, or may be used in combination with the anionic surfactant.
- an inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid
- an organic acid such as dodecylbenzenesulfonic acid, dodecylsulfuric acid, or trifluoroacetic acid
- Alkylaryl sulfonic acid represented by dodecylbenzene sulfonic acid has a function not only as an acid component but also as a surfactant, and in some cases, it is only necessary to use it alone, and it is preferably used.
- these acids and surfactants which are not limited to these, may be single or a combination of a plurality of components, respectively.
- the latex After completion of the polymerization under acidic conditions, if necessary, the latex is aged at around room temperature for several hours or more to irradiate the organopolysiloxane with a high molecular weight, and then sodium hydroxide, potassium hydroxide and sodium carbonate. Addition of an inorganic base such as ammonia, or an organic base such as alkylamine or alkylammonium hydroxide to neutralize the system to a pH of 518 to stop the polymerization of siloxane. Can be.
- an inorganic base such as ammonia
- an organic base such as alkylamine or alkylammonium hydroxide
- a surfactant that exhibits surface activity even when basic such as dodecyltrimethylammonium-demobromide and stearyltrimethylammo-demobromide
- cationic surfactants such as dialkyldimethylammonium-bromobromide such as alkyltrimethylammonium-bromobromide and didodecyldimethylammonium-bromobromide.
- a nonionic surfactant as described above can be used, or can be used in combination.
- inorganic bases such as potassium hydroxide and sodium hydroxide
- organic bases such as alkyl ammonium hydroxide
- a tetraorganoammonium hydroxide such as cetyltrimethylammonium hydroxide described in JP-A-2001-106787 has a function of both a cationic surfactant and a base, and in some cases, only that. May be used, and it is preferably used.
- bases and surfactants which are not limited to these, may be single or a combination of plural components, respectively.
- the system After completion of the polymerization under basic conditions, the system is aged as necessary, and the system is neutralized with an inorganic acid such as sulfuric acid or an organic acid such as acetic acid or dodecylbenzenesulfonic acid in the same manner as described above to form a siloxane.
- an inorganic acid such as sulfuric acid or an organic acid such as acetic acid or dodecylbenzenesulfonic acid in the same manner as described above to form a siloxane.
- an inorganic acid such as sulfuric acid or an organic acid such as acetic acid or dodecylbenzenesulfonic acid in the same manner as described above to form a siloxane.
- the average particle size of the latex organopolysiloxane (C) is preferably from 0.008 to 0.6 ⁇ m, more preferably from 0.01 to 0.3 m. It is often difficult to stably obtain particles having an average particle diameter of less than 0.008 m. If the average particle diameter is more than 0.6 m, the final molded product may have poor flame resistance and impact resistance.
- the vinyl monomer (F) used in the present invention is used for improving the flame retardant effect and the impact resistance improving effect, and has two or more polymerizable unsaturated bonds in the molecule. Containing polyfunctional monomer (D) 100-50% by weight, preferably 100-80% by weight, and other copolymerizable monomer (E) 0-50% by weight, preferably 0-20% by weight Consists of If the amount of the multifunctional monomer (D) is too small or the amount of the copolymerizable monomer (E) is too large, the impact resistance of the final graft copolymer The improvement effect tends to be lower.
- polyfunctional monomer (D) examples include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and dibutylbenzene. These may be used alone or in combination of two or more.
- the copolymerizable monomer (E) include, for example, aromatic butyl monomers such as styrene and ⁇ -methylstyrene, cyanided butyl monomers such as acrylonitrile, and acryl.
- aromatic butyl monomers such as styrene and ⁇ -methylstyrene
- cyanided butyl monomers such as acrylonitrile
- acryl examples include (meth) acrylate monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. These may be used alone or in combination of two or more.
- the vinyl monomer (G) used in the present invention can be used as a thermoplastic resin by ensuring compatibility between the organopolysiloxane-containing daraft copolymer (A) and the thermoplastic resin. It is a component used to uniformly disperse the graft copolymer.
- Specific examples of the monomer include the same as the other copolymerizable monomer (E) in the vinyl monomer (F). These may be used alone or in combination of two or more.
- carboxyl group-containing monomer such as itaconic acid, (meth) acrylic acid, fumaric acid, and maleic acid
- epoxy group-containing monomer such as glycidyl methacrylate, 2-hydroxyl methacrylate, acrylic
- a functional group-containing vinyl polymer such as a hydroxyl group-containing polymer such as 4-hydroxybutyl acid may be used in combination.
- the radical polymerization initiator used in the polymerization of the vinyl monomer (F) and the vinyl monomer (G) is not particularly limited.
- 2,2'-azobisisobutyl-tolyl In addition to thermal decomposition initiators such as potassium sulfate, organic peracids such as t-butyl peroxyisopropyl carbonate, peroxide at the mouth of paramenthane, peroxide at the mouth of cumene hydride, t-butyl peroxide and t-hexyl oxide
- Peroxides such as inorganic peroxides such as hydrogen peroxide and potassium persulfate; reducing agents such as sodium formaldehyde sulfoxylate and glucose; and, if necessary, iron (II) sulfate and the like.
- a redox-type initiator system combined with a transition metal salt and, if necessary, a chelating agent such as disodium ethylenediaminetetraacetate.
- Door can be.
- a redox type initiator system the polymerization can be carried out at a low temperature at which the peroxidized product does not substantially thermally decompose, and the polymerization temperature can be set within a wide range, which is preferable. .
- the amount of the radical polymerization initiator used is preferably 0.005 parts by weight, more preferably 0.01 parts by weight, and even more preferably 0.01 part by weight, based on 100 parts by weight of the vinyl monomer (F) used. It is at least 04 parts by weight, preferably at least 20 parts by weight, more preferably at least 10 parts by weight, and even more preferably at most 5 parts by weight. If the amount of the radical polymerization initiator is small, the reaction rate tends to be low and the production efficiency tends to be poor. If the amount is too large, the heat generation during the reaction becomes large and the production becomes difficult, or the strength of the finally obtained molded body is reduced. Tends to decrease. The same applies to the vinyl monomer (G).
- t A chain transfer agent such as dodecyl mercaptan can be preferably used in an amount of 5 parts by weight or less.
- the polymerization of the vinyl monomer (F) and the butyl monomer (G) is preferably performed by emulsion polymerization.
- the solid concentration of the latex of the organopolysiloxane-containing graft copolymer (A) to be obtained is preferably at least 10% by weight, more preferably at least 20% by weight, from the viewpoint of productivity. Is 30% by weight or more, and the viewpoint of stability of the latex is preferably 70% by weight or less, more preferably 55% by weight or less.
- Conditions such as polymerization temperature, pressure, and deoxygenation for the polymerization here can be those known to those skilled in the art.
- a divalent compound such as calcium chloride, magnesium chloride, magnesium sulfate, and aluminum chloride is used.
- the aqueous medium can be separated by heat treatment, dewatering and drying after solidification (coagulation method).
- the above divalent or higher valent metal salts are particularly economical and inexpensive, and furthermore, from the viewpoints of safety in handling and consideration of the environment, alkaline earths represented by Shiridani calcium and Shiridani magnesium. It is preferable to use a metal halide salt or magnesium sulfate.
- the organopolysiloxane-containing graft copolymer (A) used for the resin composition of the present invention recovered by force is used in the present invention, but the copolymer composition of the present invention has a halogen atom content,
- the chlorine atom content is 100 ppm or less, preferably 700 ppm or less, more preferably 400 ppm or less, and even 200 ppm or less
- the alkaline earth metal content, particularly the calcium atom content and / or the magnesium atom content is 3000 ppm. It is preferable that the control is performed so as to be not more than 2000 ppm, preferably not more than 1700 ppm, and more preferably not more than 100 ppm.
- the flame retardancy is sufficiently exhibited, which is not preferred.
- a smaller amount of alkaline earth metal is preferred in terms of flame retardancy, but the effect of improving flame retardant performance tends to saturate at a certain amount.
- the amount exceeds 200 ppm, more preferably 250 ppm or more, even more preferably 300 ppm or more, in terms of increase in the amount of washing solvent (water or alcohol) used. May be 400 ppm or more.
- the method for reducing the content of halogen atoms and the content of alkaline earth metal atoms to the above-mentioned values is not limited, but it is preferable to carry out a washing treatment with a solvent.
- the solvent is preferably water or alcohol having 4 or less carbon atoms, such as methanol, ethanol, or isopropyl alcohol, particularly water or methanol in order to increase the washing efficiency.
- methanol ethanol
- isopropyl alcohol particularly water or methanol
- washing with a solvent is preferably carried out using water and Z or methanol. It is also a preferred embodiment that the rough graft copolymer satisfies these values.
- the solvent preferably water and A method of redispersing in Z or methanol, followed by filtration and drying can be employed.
- the solvent preferably water and A method of redispersing in Z or methanol, followed by filtration and drying.
- a good powder may be obtained by re-dispersing and filtering in water after using the solvent.
- the amount of the solvent, preferably water, used is preferably 70 times or less, more preferably 50 times or less, because of the problem of increasing the amount of wastewater treatment.
- the temperature of the solvent such as water used for the washing and re-dispersion is not particularly limited, and the use of a solvent at room temperature is preferable because equipment for temperature control can be omitted.
- the use of high-temperature water causes secondary coagulation of the organopolysiloxane-containing graft copolymer (A), resulting in poor handling of the dispersion and coarse particles. It is preferable to use water at a temperature of preferably less than 40 ° C., more preferably 35 ° C. or less, and furthermore, room temperature, because the properties of the obtained powder may be deteriorated as the powder increases.
- a slightly water-soluble organic solvent such as methyl ethyl ketone is added to a latex containing an organopolysiloxane-containing graft copolymer (A).
- the obtained powder is further redispersed in a solvent such as water, methanol or ethanol. After that, it is preferable to wash by a method such as filtration and drying.
- the flame retardancy can be synergistically improved.
- the alkali metal salt (B) may be used alone or in combination of two or more.
- the alkali metal salt (B) of the sulfur-containing organic compound preferably includes a metal salt of sulfonic acid, a metal salt of monoester sulfate, and a metal salt of sulfonamide.
- metal sulfonic acid salts are preferably used, and metal (alkyl) aromatic sulfonic acid salts, metal perfluoroalkanesulfonic acid salts, and metal aliphatic sulfonic acid salts are particularly preferable.
- metal salts of diarylsulfonsulfonic acid and metal salts of alkyl sulfates examples include sodium, potassium, lithium, rubidium, cesium and the like, and preferably sodium or potassium is used.
- sulfonamide metal salt examples include sodium salt of saccharin, N- (p-tolyls) (Alkyl) sodium salt of p-toluenesulfonimide, sodium salt of N- ( ⁇ 'benzylaminocarbol) sulfalimide, sodium salt of ⁇ - (phenylcarboxyl) -sulfalimide, etc .; (alkyl )
- metal salts of aromatic sulfonic acids sodium dodecylbenzenesulfonate, sodium paratoluenesulfonate, sodium dichlorobenzenesulfonate, sodium benzenesulfonate, and the like
- metal salts of perfluoroalkanesulfonic acid include: Potassium perfluorobutanesulfonate, potassium perfluoromethylbutanesulfonate, etc .; as metal salts of aliphatic sulfonic acids, sodium dode
- the alkali metal salt ( ⁇ ) of the sulfur-containing organic compound is used in an amount of 0.02 parts by weight or more (preferably 0.05 parts by weight or less) per 100 parts by weight of the organopolysiloxane-containing daraft copolymer ( ⁇ ). Above, more preferably at least 0.1 part by weight) and at most 3.5 parts by weight (preferably at most 2 parts by weight, more preferably at most 1.0 part by weight).
- an improvement effect is particularly observed when the composition is used in a specific content of the present invention.
- the effect of lowering the strength of the resin composition may be observed in some cases, but the effect of improving the flame retardancy is excellent, and the strength and flame retardancy are improved.
- a preferable range for balancing the properties is the above range. If the amount is less than the above range, the effect of improving the flame retardancy is small, or if it is almost too small, the flame retardancy deteriorates, which is not preferable.
- the organopolysiloxane-containing graft copolymer composition of the present invention can be used by being blended with a resin such as a thermoplastic resin, a thermosetting resin, or an elastomer, and is preferably a thermoplastic resin. Or a flame retardant for thermosetting resins.
- a resin such as a thermoplastic resin, a thermosetting resin, or an elastomer
- the resin composition in which the organopolysiloxane-containing graft copolymer composition of the present invention is blended with a thermoplastic resin or a thermosetting resin has a high degree of flame retardancy and resistance to the final molded article. It can be used as a flame-retardant resin composition capable of imparting impact properties.
- the amount of the organopolysiloxane-containing graft copolymer composition of the present invention relative to the thermoplastic resin or the thermosetting resin is 0.1 parts by weight or more per 100 parts by weight of the resin. Preferably it is 1 part by weight or more and 20 parts by weight or less, preferably 10 parts by weight or less, more preferably 6 parts by weight or less. If it exceeds the above range, flame retardancy will not be exhibited, and if it is a thermoplastic resin, the fluidity during melting may decrease.If it is below the range, both flame retardancy and impact resistance will be exhibited. However, there is a tendency and it is preferable.
- thermoplastic resin or the thermosetting resin particularly when a polycarbonate resin is used, flame retardancy is easily exhibited, which is suitable.
- the polycarbonate resin is a concept containing 50% by weight or more of the polycarbonate resin with respect to the total amount of the polycarbonate resin and other resins, and preferably contains 70% by weight or more of the polycarbonate resin. Is most preferred when alone.
- that the polycarbonate resin is substantially used alone means that at least 95% by weight or more of the polycarbonate resin is contained.
- polycarbonate resin a copolymer such as polyester polycarbonate resin can be used. Is the same as above.
- Other resins contained in polycarbonate resins include polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, acrylonitrile styrene copolymer resin, butadiene styrene copolymer (HIPS) resin, and the like.
- ABS Acrylonitrile butadiene rubber Styrene copolymer
- AAS acrylonitrile acrylic rubber styrene copolymer
- the organopolysiloxane-containing graft copolymer composition of the present invention is mixed with a thermoplastic resin or a thermosetting resin by mixing with a Henschel mixer, ribbon blender, or the like, and then using a roll, an extruder, or the like. It can be performed by melt-kneading with a kneader or the like.
- compounding agents that is, antioxidants, anti-dripping agents, polymer processing aids, flame retardants, impact modifiers, plasticizers, lubricants, ultraviolet absorbers, pigments, glass fibers , Fillers, polymeric lubricants and the like can be blended.
- fluorine resin such as polytetrafluoroethylene and polyvinylidene fluoride can be used as an anti-dripping agent at the time of combustion test such as UL-94 test. 2 parts by weight or less, more preferably 1 part by weight or less, more preferably 0.6 parts by weight or less, preferably 0.1 part by weight or more per 100 parts by weight of fat or thermosetting resin. If a problem arises, it is preferable because the prevention effect can be obtained.
- the flame-retardant resin composition of the present invention may be molded by using a usual thermoplastic resin composition when obtained from the organopolysiloxane-containing graft copolymer composition and the thermoplastic resin.
- a usual thermoplastic resin composition when obtained from the organopolysiloxane-containing graft copolymer composition and the thermoplastic resin.
- injection molding, extrusion molding, blow molding, calender molding, and the like can be applied.
- the resin composition is obtained from a thermosetting resin
- a method in which the flame-retardant resin composition of the present invention is introduced into a mold or the like and then cured by heating or the like can be applied.
- the obtained molded article is excellent in impact resistance and flame retardancy.
- the latex was dried in a hot air drier at 120 ° C. for 1 hour to determine the amount of solid components, and was calculated as 100 ⁇ the amount of solids formed and the amount of charged monomers (%).
- the volume average particle diameter of the seed polymer, the organopolysiloxane particles and the graft copolymer was measured in the state of a latex.
- the volume average particle diameter ( ⁇ m) was measured using a MICRO TRAC UPA150 manufactured by Nikkiso Co., Ltd. as a measuring device.
- otatamethyltetracyclosiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were determined by analysis, and the ratio of the total amount to the resin solid content was defined as the volatile siloxane content.
- 3 g of the powder was quantitatively analyzed in a helium atmosphere using a SPECTORO energy dispersive X-ray fluorescence analyzer XEPOS manufactured by Rigaku Corporation.
- the organopolysiloxane-containing graft copolymer after redispersion and filtration by adding a solvent is dried by standing, and the obtained dry powder is classified with a sieve having an opening of 0.45 mm. Weight) / (sieving, total weight before) (percent) was defined as the amount of coarse particles.
- a mixed solution of 90 parts by weight of a rate, 27 parts by weight of t-decyl mercaptan, and 0.09 parts by weight (solid content) of paramenthane hydroperoxide was continuously added over 3 hours. After that, post-polymerization was performed for 2 hours, and a latex containing a seed polymer (SD-1) having a particle size of 0.03 ⁇ m and a polymerization conversion of 90% (t-dodecylmer force butane was regarded as a raw material component) was used. Obtained.
- SD-1 seed polymer having a particle size of 0.03 ⁇ m and a polymerization conversion of 90%
- the mixture was stirred with a homomixer at 7500 rpm for 5 minutes to prepare a siloxane emulsion.
- a seed polymer (SD-1) latex corresponding to the solid content in the amount shown in Table 1 was charged into a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer addition port, and thermometer. It is. The siloxane emulsion was added to the flask in a lump.
- the temperature was increased from 35 ° C to 80 ° C over 1 hour while stirring the system under a nitrogen stream, and then 1 part by weight of 10% dodecylbenzenesulfonic acid (DBSA, manufactured by Kao Corporation, Neoberex GS) aqueous solution (Solids) was added.
- DBSA dodecylbenzenesulfonic acid
- the pH of the system was adjusted to 6.5 with a 3% aqueous sodium hydroxide solution to terminate the polymerization, and organopolysiloxane particles (S-1, A latex containing 2) was obtained.
- Table 1 shows the results obtained by measuring the polymerization conversion rate and the particle diameter of the latex of the organopolysiloxane particles.
- Example 1 2 3 4 5 6 7 8 9 10 11 12 year old Luganopolysiloxane-containing 'raft kid's union composition SGC-1 SGC-2 SGC-3 SGC-4 SGC-5 SGC-6 SGC-7 SGC- 8 SGC-9 SGC-10 SGC-11 SGC-12 Organopolis
- Example 6 Organopolysiloxane-Based Graft Copolymer Composition (SGC-6) Addition of Methanol After 'stirring' filtration, water was again added and stirred 'drying without filtration. In the same manner as in Example 5, an organopolysiloxane-based graft copolymer composition (SGC-6) was obtained. Table 3 shows the results of the quantitative analysis of the chlorine atom and calcium atom contents and the amount of coarse particles.
- An organopolysiloxane-based graft copolymer composition (SG-1) was prepared in the same manner as in Example 1 except that the amount of methanol and water added and the amount of sodium nitrate dodecylbenzenesulfonate added were as shown in Table 4.
- Table 4 shows the results of the quantitative analysis of the chlorine atom and calcium atom contents and the amount of coarse particles.
- Example 7 The same procedure as in Example 7 was carried out except that the amount of washing water at the time of dehydration and the amount of sodium dodecylbenzenesulfonate added as shown in Table 5 were used, and the organopolysiloxane-based graft copolymer composition (SGC'-8-11) was used. ). Table 5 shows the results of quantitative analysis of the content of chlorine and calcium atoms and the results of the amount of coarse particles.
- Example 11 to 12 or Comparative Example 11 to 11 Obtained organopolysiloxane-based graft copolymer yarn and composition (SGC-1) — 12, 30-1-11) 3 parts by weight of polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., trade name: Polyflon FA—500) 0.4 parts by weight of polycarbonate resin (Teijin Chemicals Co., Ltd.) Made by the company, trade name: Panlite L1225WX) It was blended to 100 parts by weight. The obtained compound was melt-mixed at 270 ° C.
- Example 13 14 15 16 17 18 19 20 21 22 23 24 Polycarbonate part 100 100 100 100 100.
- Example Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Polycarbonate 1 part 100 100 100 100 100 100 100 100 100 100 Organopolysiloxane-containing graft copolymer composition SGC 1 SGC-2 SGC-3 SGC-4 SGC-5 SGC-6 SGC-7 SGC '-8
- SDBS Sodium dodecylbenzenesulfonate
- D4 1,3,5,7-otatamethylcyclotetrasiloxane
- DHPDMS 0.7% by weight of low-molecular-weight siloxane containing 10 or less silicon atoms
- A1MA aryl metathallate
- CaCl is calcium chloride
- H O Indicates ion-exchanged water.
- the washing solvent MeOHZHO means that water was used after washing with methanol.
- the comparative example was excellent in only one of the flame retardancy and the impact resistance, or both were not good, whereas the examples were not. It can also be seen that both the flame retardancy and the impact resistance are excellent.
- the use of the molded article obtained from the flame-retardant resin composition of the present invention is not particularly limited.
- flame-retardant products such as desktop computers, notebook computers, printers, and copiers are used. Uses that require properties are listed.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/592,736 US20080242797A1 (en) | 2004-03-15 | 2005-03-03 | Organopolysiloxane-Containing Graft Copolymer Composition |
EP05719936A EP1731568A1 (en) | 2004-03-15 | 2005-03-03 | Organopolysiloxane-containing graft copolymer composition |
CA002559929A CA2559929A1 (en) | 2004-03-15 | 2005-03-03 | Organopolysiloxane-containing graft copolymer composition |
JP2006510923A JPWO2005087866A1 (en) | 2004-03-15 | 2005-03-03 | Organopolysiloxane-containing graft copolymer composition |
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JP2004073565 | 2004-03-15 | ||
JP2004-073565 | 2004-03-15 |
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WO2005087866A1 true WO2005087866A1 (en) | 2005-09-22 |
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PCT/JP2005/003632 WO2005087866A1 (en) | 2004-03-15 | 2005-03-03 | Organopolysiloxane-containing graft copolymer composition |
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US (1) | US20080242797A1 (en) |
EP (1) | EP1731568A1 (en) |
JP (1) | JPWO2005087866A1 (en) |
KR (1) | KR20060135725A (en) |
CN (1) | CN1930236A (en) |
CA (1) | CA2559929A1 (en) |
TW (1) | TW200606205A (en) |
WO (1) | WO2005087866A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007326895A (en) * | 2006-06-06 | 2007-12-20 | Shin Etsu Chem Co Ltd | Additive for making organic resin of flame retardance, flame retardant resin composition and molded article of the same |
WO2009131068A1 (en) * | 2008-04-25 | 2009-10-29 | 株式会社カネカ | Polyorganosiloxane-containing graft copolymer, and resin composition containing the copolymer |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2015140671A1 (en) * | 2014-03-20 | 2015-09-24 | Sabic Global Technologies B.V. | Polycarbonate compositions, methods of their manufacture, and articles thereof |
WO2018106464A1 (en) | 2016-12-09 | 2018-06-14 | Sabic Global Technologies B.V. | Polyetherimide composition and associated article and additive manufacturing method |
EP3546520A1 (en) | 2018-03-28 | 2019-10-02 | SABIC Global Technologies B.V. | Impact modified polyestercarbonate-polysiloxane composition and associated article and additive manufacturing method |
EP3663367A1 (en) | 2018-12-05 | 2020-06-10 | SABIC Global Technologies B.V. | Core-shell filament, method of forming a core-shell filament, method of forming an article by fused filament fabrication, and article formed thereby |
EP3771723A1 (en) | 2019-07-31 | 2021-02-03 | SHPP Global Technologies B.V. | Additive manufacturing article and method |
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- 2005-03-03 CN CNA2005800079830A patent/CN1930236A/en active Pending
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Also Published As
Publication number | Publication date |
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JPWO2005087866A1 (en) | 2008-01-24 |
EP1731568A1 (en) | 2006-12-13 |
TW200606205A (en) | 2006-02-16 |
KR20060135725A (en) | 2006-12-29 |
CA2559929A1 (en) | 2005-09-22 |
US20080242797A1 (en) | 2008-10-02 |
CN1930236A (en) | 2007-03-14 |
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